Supporting online information Lewis acid enhancement by ... · S1 Supporting online information...

S1

Supporting online information

Lewis acid enhancement by juxtaposition with an onium ion:

The case of a mercury stibonium complex

Tzu-Pin Lin,a Ryan C. Nelson,

b Tianpin Wu,

bJeffrey T. Miller*

b and François P. Gabbaï*

a

a Department of Chemistry, Texas A&M University, College Station, TX 77843-3255.

b Chemical Sciences and Engineering Division, Argonne National Laboratory,

Argonne, IL 60439-4837.

RECEIVED DATE

*To whom correspondence should be addressed. E-mail: [email protected]

Electronic Supplementary Material (ESI) for Chemical ScienceThis journal is © The Royal Society of Chemistry 2012

S2

This PDF file includes:

Titration experiments

Fig. S1 1H NMR titration spectra of [2]

+ vs TBABr.

Fig. S2 199

Hg titration spectra of [2]+ vs TBAI, TBABr, and TBACl.

Derivation of the equation used to determine the 1:2 stability constant.

Computational section

Fig. S3 NBO plots showing 5d(Hg)→*(Sb-CPh1) interactions for [2]+, 2-F, [2-Cl2]

-,

and 2-I.

DFT optimized structural coordinates

X-ray Absorption Spectroscopy

Table S1 X-ray Absorption Spectra Fits.


S3

Titration experiments

General considerations. NMR spectra were recorded on Varian Unity Inova 400

FT NMR (399.59 MHz for 1H, 375.96 MHz for

19F, 100.45 MHz for

13C, 71.20 MHz

for 199

Hg) spectrometers at ambient temperature. Chemical shifts (given in ppm) are

referenced to residual 1H and

13C solvent signals, BF3-Et2O, and external neat HgMe2.

Fig. S1: 1H Spectra obtained by titrating [2]

+ against TBABr in DMSO-d6. The

concentration in [2]+ remained constant during the titration (2.23 × 10

-2 M).


S4

Fig. S2: 199

Hg spectra obtained by titrating [2]+ against TBAI, TBABr, and TBACl in

DMSO-d6. The concentration in [2]+ remained constant during the titrations (2.20 ×

10-2

M (left), 2.23 × 10-2

M (middle), and 2.23 × 10-2

M (right)).


S5

Derivation of the equation used to determine the chloride binding constants: (R =

2+, S = Cl

-)


S6


S7

Computational section

Fig. S3: NBO plots showing the 5d(Hg)→*(Sb-CPh1) interactions for [2]+, 2-F,

[2-Cl2]-, and 2-I.


S8

DFT optimized structural coordinates

Complex [2]+

Method 1

Hg -0.227550 -2.039756 -0.137530

Sb 0.116902 1.043079 -0.080034

C -4.601759 -2.536969 -0.429023

H -5.299097 -3.369892 -0.290284

C 0.430868 3.931792 -1.282871

H 0.359810 3.443372 -2.262396

C -4.149616 -0.224987 -1.090259

C 3.931278 -3.488483 -0.412790

H 4.427621 -4.454549 -0.272586

C -3.793228 2.094331 -1.775976

H -4.166832 3.041993 -2.176520

C -2.432265 1.989634 -1.389667

H -1.806990 2.881986 -1.472930

C -2.299814 -1.675558 -0.296006

C -1.919564 0.795855 -0.881582

C 1.241835 0.204044 2.679389

H 2.199498 0.164893 2.148397

C -2.743818 -0.382802 -0.743284

C 4.000382 -1.134904 -1.078410

C 1.875605 -2.140713 -0.282933

C 0.049400 0.530339 2.000994

C 2.594603 -0.978469 -0.731101

C 0.456451 3.834184 1.160723


S9

H 0.404534 3.265013 2.095316

C 0.360121 3.184717 -0.085390

C -5.046550 -1.320049 -0.913512

H -6.100977 -1.174122 -1.174785

C 2.049887 0.351998 -0.874572

C -4.634436 1.010280 -1.609092

H -5.695927 1.084557 -1.872393

C 4.633702 -2.400500 -0.899125

H 5.694227 -2.491472 -1.160649

C 0.691411 5.973508 0.018439

H 0.820609 7.060026 0.059466

C 2.811349 1.402190 -1.387758

H 2.395948 2.409356 -1.475543

C -3.222903 -2.710740 -0.138461

H -2.887362 -3.696279 0.205804

C 4.744109 -0.038420 -1.602691

H 5.795494 -0.200591 -1.867145

C 0.596347 5.325513 -1.224487

H 0.651070 5.902689 -2.153593

C 2.547694 -3.353800 -0.123597

H 2.002689 -4.241230 0.219703

C -1.184903 0.560545 2.682308

H -2.114514 0.800347 2.153910

C -1.218812 0.265882 4.055406

H -2.174599 0.288044 4.589598

C 1.192472 -0.088829 4.052556

H 2.115339 -0.343493 4.584402

C 4.161638 1.203473 -1.774330

H 4.733941 2.043787 -2.179768

C 0.622007 5.229607 1.206316

H 0.696830 5.732394 2.176340

C -0.033929 -0.058320 4.737790

H -0.066652 -0.289493 5.807721

Method 2

Hg 0.133678 -2.059312 -0.207841

Sb -0.066562 1.028608 -0.004888

C -4.023420 -3.363333 -0.573567


S10

H -4.541686 -4.319282 -0.506049

C -0.237722 3.834899 -1.394200

H -0.200840 3.275874 -2.329900

C -4.035643 -0.975611 -1.054267

C 4.431920 -2.816354 -0.475146

H 5.068132 -3.696683 -0.390252

C -4.139884 1.400751 -1.563282

H -4.690373 2.283241 -1.886478

C -2.780476 1.528969 -1.199728

H -2.338357 2.522010 -1.226605

C -1.950309 -2.087478 -0.355738

C -2.046942 0.429719 -0.782836

C 1.167580 0.563351 2.781317

H 2.113332 0.706761 2.257053

C -2.629148 -0.883818 -0.718457

C 4.144685 -0.449663 -0.973828

C 2.206698 -1.819391 -0.308808

C -0.055181 0.607452 2.096586

C 2.731840 -0.539442 -0.665717

C -0.250760 3.912739 1.040275

H -0.223009 3.411157 2.008489

C -0.200838 3.179077 -0.151564

C -4.697139 -2.229654 -0.965749

H -5.756873 -2.273566 -1.220167

C 1.986057 0.687183 -0.750276

C -4.752921 0.173894 -1.477480

H -5.807951 0.064625 -1.733122

C 4.961117 -1.606858 -0.862516

H 6.022555 -1.514365 -1.095733

C -0.374235 5.965519 -0.245292

H -0.442683 7.053374 -0.281140

C 2.578242 1.870091 -1.162635

H 2.011426 2.797084 -1.205429

C -2.642699 -3.286632 -0.282333

H -2.121247 -4.204417 -0.006998

C 4.714874 0.780943 -1.392764

H 5.780013 0.808262 -1.627420

C -0.323487 5.229332 -1.434561


S11

H -0.351087 5.739402 -2.397526

C 3.047016 -2.918179 -0.212715

H 2.643225 -3.894700 0.058095

C -1.271464 0.405904 2.764343

H -2.220532 0.427024 2.227039

C -1.257078 0.165143 4.141457

H -2.197790 0.004821 4.668432

C 1.165406 0.321711 4.158290

H 2.111616 0.283301 4.698284

C 3.949481 1.917221 -1.500588

H 4.386905 2.861718 -1.821297

C -0.337587 5.308874 0.987263

H -0.376711 5.879335 1.915574

C -0.042838 0.123043 4.835182

H -0.037773 -0.070986 5.908333


S12

Complex 2-F

Method 1

Hg 0.002060 -2.041331 -0.129415

Sb 0.002978 1.110999 -0.397457

F 0.015116 1.855679 -2.325271

C -2.110002 -1.950890 -0.195829

C -2.053668 0.493347 -0.942844

C 4.196783 -0.753863 -0.819133

C -0.016666 0.358711 1.709720

C -2.744532 -0.735127 -0.638203

C 2.754079 -0.736032 -0.621825

C -4.135927 1.522349 -1.731640

H -4.641986 2.389153 -2.170874

C 0.002423 3.194073 0.219738

C 2.114201 -1.955333 -0.196807

C 1.189961 0.180215 2.421224

H 2.152847 0.291152 1.909344

C 4.159526 1.533138 -1.672579

H 4.670823 2.404994 -2.095400

C 2.068572 0.498444 -0.914090

C -4.848569 0.390980 -1.378940

H -5.935457 0.345619 -1.521428

C -2.888358 -3.074095 0.086118

H -2.408861 -4.003088 0.419272

C 0.003019 3.552470 1.580675

H 0.003311 2.784440 2.360469


S13

C -4.302262 -3.064941 -0.057919

H -4.882690 -3.964030 0.179643

C 1.176719 -0.152441 3.787435

H 2.123594 -0.291916 4.322329

C -4.186032 -0.751276 -0.843235

C 0.002643 4.198859 -0.770153

H 0.003843 3.894951 -1.820990

C -2.735217 1.569728 -1.509483

H -2.178682 2.461753 -1.806816

C -4.931480 -1.926615 -0.529100

H -6.017370 -1.910190 -0.684484

C 4.866257 0.393960 -1.333751

H 5.953744 0.346913 -1.470960

C 2.887791 -3.084948 0.072472

H 2.403984 -4.016601 0.391680

C 2.757477 1.581099 -1.459452

H 2.207191 2.479987 -1.747630

C 4.937022 -1.935937 -0.518290

H 6.023745 -1.920328 -0.667689

C -1.237413 0.215498 2.404842

H -2.189620 0.353857 1.879774

C 0.002652 5.552378 -0.395271

H 0.002622 6.329670 -1.168339

C 0.003337 4.909531 1.948189

H 0.003805 5.182933 3.009730

C 4.302169 -3.078956 -0.066549

H 4.878648 -3.983252 0.160630

C 0.002827 5.909550 0.962990

H 0.002853 6.966373 1.254068

C -1.252691 -0.116752 3.770847

H -2.210409 -0.228253 4.292799

C -0.045069 -0.304617 4.463741

H -0.056095 -0.564766 5.528461

Method 2

Hg 1.183400 -0.191889 -3.659187

Sb 3.304930 1.841171 -2.743737

F 1.822159 2.013554 -1.321460


S14

C 2.115364 -1.642186 -2.468643

C 3.830039 0.008267 -1.572583

C 0.037658 3.682638 -5.453287

C 4.624773 1.344538 -4.458105

C 3.222286 -1.289773 -1.633064

C 0.762181 2.666583 -4.717115

C 5.401657 -0.765361 0.129169

H 6.231185 -0.534124 0.797872

C 4.506627 3.347399 -1.764287

C 0.283223 1.319751 -4.795235

C 4.514907 2.053021 -5.663369

H 3.762590 2.835374 -5.776002

C 1.539167 5.410763 -4.640478

H 1.855697 6.452830 -4.587013

C 1.902061 3.093999 -3.959226

C 4.857526 -2.025380 0.090667

H 5.247393 -2.821257 0.728291

C 1.610358 -2.934271 -2.453086

H 0.763688 -3.200859 -3.089252

C 5.751321 3.724995 -2.282455

H 6.136020 3.263673 -3.193603

C 2.157400 -3.935859 -1.618235

H 1.735616 -4.941369 -1.625066

C 5.363622 1.756836 -6.736429

H 5.266769 2.312111 -7.670611

C 3.771206 -2.319419 -0.774969

C 4.013209 3.941972 -0.595129

H 3.040875 3.634646 -0.208699

C 4.881791 0.251004 -0.708115

H 5.336946 1.237716 -0.650646

C 3.215182 -3.626790 -0.794667

H 3.645766 -4.382779 -0.135571

C 0.450507 5.041273 -5.393381

H -0.118164 5.785517 -5.954554

C -0.825232 1.014383 -5.571177

H -1.190149 -0.013275 -5.627470

C 2.264247 4.427660 -3.923957

H 3.124620 4.752542 -3.340769


S15

C -1.093673 3.316088 -6.231984

H -1.622434 4.100252 -6.777035

C 5.583476 0.327252 -4.343450

H 5.670919 -0.246263 -3.419462

C 4.773993 4.918038 0.056595

H 4.392067 5.381354 0.967500

C 6.506779 4.702617 -1.624173

H 7.477379 4.996178 -2.026627

C -1.519352 2.008777 -6.297241

H -2.389524 1.738291 -6.895835

C 6.018610 5.298804 -0.456724

H 6.609115 6.061545 0.053714

C 6.432252 0.032740 -5.416991

H 7.173002 -0.762346 -5.316886

C 6.323104 0.746869 -6.614201

H 6.978617 0.510854 -7.454329


S16

Complex [2-Cl2]-

Method 1

Hg -1.954028 0.071533 -0.221871

Sb 1.089892 -0.056423 -0.219456

Cl -4.660895 0.190922 -0.278491

Cl 0.917517 -0.169540 -2.996917

C 0.879203 2.130266 -0.544437

C -1.829405 -2.089690 -0.168254

C -0.357571 2.832334 -0.373691

C -1.635209 2.210138 -0.153713

C 2.070895 2.790918 -0.816460

H 2.997574 2.228765 -0.964119

C 4.016680 -0.093881 0.931916

H 3.493711 -0.002804 1.890442

C 3.284091 -0.148308 -0.271229

C 0.896007 0.049056 1.979690

C 1.039882 1.280703 2.653159

H 1.242364 2.195681 2.084182

C 0.706069 -2.239475 -0.367841

C 0.542779 -5.049819 -0.414747

H 0.460820 -6.144694 -0.427611

C 0.915460 1.354937 4.051509

H 1.028704 2.321836 4.557359

C -0.598356 -2.825655 -0.276282

C 0.488084 -1.033313 4.137553

H 0.263450 -1.941458 4.710421


S17

C -0.652459 -4.284674 -0.283753

C 0.951872 4.938014 -0.710862

H 0.964332 6.034783 -0.762252

C -3.029609 -2.791427 -0.040627

H -3.965669 -2.225825 0.032564

C 1.853616 -3.013853 -0.490387

H 2.836787 -2.542656 -0.575733

C 0.617219 -1.105990 2.739253

H 0.485876 -2.071991 2.238406

C 1.774777 -4.432121 -0.522075

H 2.693273 -5.021940 -0.626863

C -3.076491 -4.211705 -0.028415

H -4.043642 -4.720544 0.072393

C -2.753543 3.017760 0.061424

H -3.728590 2.541090 0.214547

C 2.108706 4.208303 -0.914036

H 3.058206 4.709182 -1.137910

C 5.421665 -0.154003 0.913674

H 5.979279 -0.111578 1.857426

C 3.978031 -0.261607 -1.494237

H 3.405935 -0.302220 -2.429713

C 0.638032 0.197434 4.797087

H 0.533908 0.255489 5.887413

C -1.909808 -4.943259 -0.157069

H -1.926067 -6.041361 -0.165717

C -1.464364 5.058999 -0.209314

H -1.387653 6.153681 -0.252922

C -0.286069 4.288819 -0.431328

C -2.672730 4.436744 0.048570

H -3.578031 5.032031 0.223182

C 6.107504 -0.267264 -0.306088

H 7.203381 -0.313669 -0.319798

C 5.382774 -0.320342 -1.508319

H 5.910899 -0.408644 -2.465817

Method 2

Hg 1.333899 0.043206 1.448324

Sb -0.683752 0.294600 -0.813833


S18

Cl 3.114192 -0.337901 3.485387

Cl -0.059137 2.875277 -0.731111

C 1.154969 0.082778 -2.043082

C -0.325711 0.476743 2.734456

C 2.447834 -0.194878 -1.507869

C 2.760833 -0.299767 -0.114110

C 0.932422 0.187685 -3.402461

H -0.063971 0.406744 -3.785537

C -2.842239 -0.440806 -2.985639

H -2.700941 -1.446617 -2.587171

C -2.116729 0.636424 -2.456180

C -1.031448 -1.905478 -0.688650

C -0.354499 -2.785924 -1.547466

H 0.368006 -2.400190 -2.269020

C -2.039818 0.765999 0.884429

C -4.006609 1.353803 2.791711

H -4.761598 1.584398 3.547402

C -0.590259 -4.164372 -1.488055

H -0.051641 -4.834331 -2.161442

C -1.644556 0.763808 2.254916

C -2.171211 -3.814568 0.307039

H -2.873320 -4.209731 1.044002

C -2.682989 1.072702 3.223277

C 3.253363 -0.272188 -3.866167

H 4.082090 -0.413734 -4.564359

C -0.077983 0.506856 4.099796

H 0.932183 0.286381 4.451337

C -3.336345 1.043391 0.496673

H -3.612697 1.040025 -0.557375

C -1.936469 -2.435841 0.243328

H -2.463911 -1.773350 0.931859

C -4.333922 1.339083 1.455856

H -5.350770 1.555148 1.124778

C -1.090905 0.815520 5.037582

H -0.850969 0.833706 6.102777

C 4.063229 -0.587721 0.269881

H 4.288974 -0.659263 1.335904

C 1.988919 0.010800 -4.327562


S19

H 1.788284 0.099373 -5.396325

C -3.753965 -0.237184 -4.028421

H -4.311814 -1.085183 -4.430718

C -2.316546 1.921602 -2.980748

H -1.751669 2.757635 -2.563575

C -1.500636 -4.682058 -0.560927

H -1.678044 -5.758458 -0.507176

C -2.368744 1.092174 4.607426

H -3.163112 1.332640 5.318466

C 4.829829 -0.672893 -2.021882

H 5.619428 -0.807303 -2.765584

C 3.516363 -0.382147 -2.474666

C 5.097532 -0.777115 -0.675851

H 6.109407 -0.998597 -0.329974

C -3.948821 1.045190 -4.550915

H -4.659700 1.203497 -5.364968

C -3.228392 2.122684 -4.023679

H -3.375426 3.127689 -4.424785


S20

Complex 2-I

Method 1

Hg -1.438940 -0.011581 -0.402754

Sb 1.584636 0.029977 -0.033910

I -4.180415 -0.041887 0.648415

C 3.732460 0.033862 0.380725

C -1.070474 -2.130759 -0.713119

C -1.142812 2.115833 -0.736210

C 0.189657 4.116490 -1.400038

C 0.218044 -2.658910 -1.066511

C 4.155142 -0.042378 1.722251

H 3.418256 -0.097988 2.530994

C 0.840083 -0.051948 1.984571

C 6.487322 0.021148 1.020074

H 7.554324 0.016153 1.268573

C -0.039393 1.078370 3.947236

H -0.360294 1.999310 4.445991

C 0.749235 -1.292361 2.647236

H 1.033000 -2.221956 2.140603

C 4.708852 0.105243 -0.639969

H 4.412822 0.171363 -1.694544

C 0.137845 2.718746 -0.982320

C 1.409143 2.066461 -0.828397

C 1.461374 -1.943952 -0.979898

C 2.615791 2.716107 -1.077114

H 3.569804 2.207102 -0.923772


S21

C 1.439386 4.746856 -1.664850

H 1.433777 5.795107 -1.988363

C -2.291820 2.896919 -0.876662

H -3.270079 2.446303 -0.671485

C -0.863280 -4.844237 -1.580655

H -0.771453 -5.880067 -1.929808

C 6.077308 0.098394 -0.320933

H 6.821435 0.154438 -1.123428

C 0.310901 -4.037983 -1.533864

C 1.564234 -4.579825 -1.940119

H 1.589139 -5.614263 -2.304639

C 0.440881 1.135905 2.628317

H 0.480522 2.097574 2.104440

C 2.633475 4.067050 -1.510341

H 3.592424 4.559116 -1.705370

C 2.674740 -2.507832 -1.365687

H 3.610351 -1.953637 -1.263446

C 2.726288 -3.833042 -1.870311

H 3.688205 -4.256677 -2.178528

C -1.020859 4.855323 -1.538014

H -0.958702 5.904559 -1.851831

C -2.240543 4.260335 -1.272618

H -3.171240 4.831496 -1.369227

C -2.180902 -2.974893 -0.767070

H -3.163507 -2.580880 -0.481170

C -0.125591 -0.154263 4.614436

H -0.511799 -0.195244 5.638660

C 5.525410 -0.048627 2.038783

H 5.837897 -0.107758 3.087474

C 0.267020 -1.336732 3.965735

H 0.187849 -2.300665 4.480283

C -2.084974 -4.328983 -1.187444

H -2.985602 -4.953597 -1.210983

Method 2

Hg -1.444816 -0.044034 -0.368586

Sb 1.543588 0.031824 0.107986

I -4.388080 -0.216298 -0.116702


S22

C 3.727146 0.131395 -0.035901

C -1.087514 -2.044115 -1.075410

C -1.240500 2.064829 0.021557

C -0.037814 4.182350 -0.453386

C 0.196652 -2.670088 -1.020236

C 4.492280 0.424964 1.100516

H 4.011179 0.565450 2.069863

C 1.270298 0.037221 2.242934

C 6.519539 0.350682 -0.228841

H 7.604895 0.434907 -0.303028

C 1.051376 1.239653 4.327832

H 0.994831 2.183893 4.870579

C 1.165960 -1.183444 2.922484

H 1.195251 -2.129041 2.378837

C 4.369267 -0.055610 -1.271265

H 3.793282 -0.299587 -2.165440

C -0.029275 2.736848 -0.331406

C 1.226257 2.101598 -0.567267

C 1.402092 -2.066012 -0.551447

C 2.342048 2.789220 -1.006090

H 3.289097 2.278273 -1.167626

C 1.117777 4.864911 -0.917734

H 1.067655 5.949276 -1.033460

C -2.355323 2.819053 0.352131

H -3.284526 2.309185 0.609333

C -0.815287 -4.715469 -1.998749

H -0.701604 -5.748315 -2.332996

C 5.759588 0.057048 -1.366818

H 6.249355 -0.087916 -2.330672

C 0.315900 -4.051038 -1.457949

C 1.550462 -4.740574 -1.335109

H 1.596398 -5.781164 -1.661881

C 1.204298 1.252283 2.937682

H 1.259446 2.203858 2.407261

C 2.277867 4.187044 -1.215499

H 3.159090 4.715207 -1.578919

C 2.591665 -2.764691 -0.436852

H 3.490395 -2.279564 -0.061117


S23

C 2.664634 -4.125462 -0.813558

H 3.605737 -4.663611 -0.702468

C -1.213730 4.900419 -0.113379

H -1.204798 5.988409 -0.201722

C -2.340038 4.233040 0.312691

H -3.240007 4.786933 0.582863

C -2.158736 -2.746809 -1.607634

H -3.141636 -2.274985 -1.637622

C 0.956197 0.024267 5.014481

H 0.827974 0.019869 6.098063

C 5.885197 0.532056 1.003027

H 6.472474 0.756752 1.894574

C 1.010963 -1.184618 4.312857

H 0.923564 -2.133349 4.843810

C -2.026956 -4.070466 -2.086655

H -2.896550 -4.579895 -2.503363


S24

Table S1 X-ray Absorption Spectra Fits.

Sb and Hg XANES and EXAFS Fits

Sample XANES

Edge

Oxidation

State

Scatter N R, Å 2

(x

103)

Eo,

eV

Sb K-edge

30,492.0

Sb+3

Sb-C

3.1

2.14

0.0

-1.5

30,493.3

Sb+5

Sb-C

4.1

2.09

0.0

-2.0

30,493.3

Sb+5

Sb-C

4.2

2.11

0.0

-3.1

30,493.3

Sb+5

Sb-C

3.8

2.13

0.0

-1.5

30,493.2

Sb+5

Sb-C

4.1

2.08

0.0

-1.3

Hg L3 Edge


S25

12,284.6

Hg+2

Hg-C

2.0

2.09

0.0

-0.1

12,285.7

Hg+2

Hg-C

2.0

2.10

1.5

-0.5

12,285.5

Hg+2

Hg-C

1.9

2.06

1.5

-3.5

12,285.7

Hg+2

Hg-C

1.9

2.06

1.5

-2.8


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